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WO2017142782A1 - Points quantiques à copolymères fluorés stabilisants - Google Patents

Points quantiques à copolymères fluorés stabilisants Download PDF

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Publication number
WO2017142782A1
WO2017142782A1 PCT/US2017/017152 US2017017152W WO2017142782A1 WO 2017142782 A1 WO2017142782 A1 WO 2017142782A1 US 2017017152 W US2017017152 W US 2017017152W WO 2017142782 A1 WO2017142782 A1 WO 2017142782A1
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weight
parts
composite particle
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groups
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PCT/US2017/017152
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Paul B. ARMSTRONG
Saswata CHAKRABORTY
Michael C. Palazzotto
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3M Innovative Properties Company
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Priority to CN201780012130.9A priority Critical patent/CN108699433B/zh
Priority to KR1020187026237A priority patent/KR102034615B1/ko
Priority to US15/999,475 priority patent/US10899961B2/en
Publication of WO2017142782A1 publication Critical patent/WO2017142782A1/fr

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    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • C09K11/701—Chalcogenides
    • C09K11/703—Chalcogenides with zinc or cadmium
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/422—Luminescent, fluorescent, phosphorescent

Definitions

  • Quantum Dot Enhancement Films are used as part of the backlight for LCD displays. Red and green quantum dots in the film down-convert light from the blue LED source to give white light. This has the advantage of improving the color gamut over the typical LCD display and keeping the energy consumption low compared to LED displays.
  • Colloidal quantum dot nanoparticles are stabilized with organic ligands and/or additives to maintain dispersion stability in a carrier fluid (or solvent).
  • Quantum dot ligands also improve photoluminescent quantum yields by passivating surface traps, stabilize against aggregation and degradation, and influence the kinetics of nanoparticle (preferably, nanocrystal) growth during synthesis. Therefore, optimizing the organic ligand and/or additive is important for achieving optimal quantum yield, processability, and functional lifetime in QDEF.
  • Composite particles are provided that are capable of fluorescence and suitable for use in quantum dot enhancement films.
  • the present disclosure provides a composite particle that includes: a fluorescent semiconductor core/shell nanoparticle (preferably, nanocrystal); and a stabilizing copolymer combined with the core/shell nanoparticle, the stabilizing copolymer comprising a copolymer having pendent fluorochemical groups and pendent phosphine, arsine or stibine groups.
  • the co olymer has pendent stabilizing groups of the formula:
  • each R 1 is a hydrocarbyl group including alkyl, aryl, alkaryl and aralkyl;
  • R 2 is a divalent hydrocarbyl group selected from alkylene, arylene, alkaryl aralkylene;
  • Z is P, As or Sb;
  • Q 1 is a functional group selected from -CO2-, -0-, -S-, -CONR 3 -, - H-CO- R 3 -, and -NR 3 - , where R 3 is H or C1-C4 alkyl, and subscript x is 0 or 1, and
  • R 6 is a divalent hydrocarbyl group selected from alkylene, arylene, alkarylene and aralkylene.
  • copolymer has pendent fluorochemical groups of the formula:
  • Q 2 is selected from a covalent bond ("-"), -CO2-, -CONR 3 -, -NH-CO-NR 3 -, and -NR 3 -, where R 3 is H or C1-C4 alkyl;
  • Q 3 is selected from -CH2-S-, -CH2-O-, -CO2-, -CONR 3 -, -NH-CO-NR 3 -, and -NR 3 , where R 3 is H or C1-C4 alkyl,
  • subscripts g and h are independently 0 or 1;
  • R 10 is a hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene and Rf is a perfluorinated group.
  • the present disclosure provides a composite particle that includes: a fluorescent semiconductor core/shell nanoparticle (preferably, nanocrystal); and a stabilizing copolymer having 1) pendent phosphine, arsine or stibine groups, and 2) pendent fluorochemical groups, that is combined with, attached to, or associated with, the core/shell nanoparticle.
  • a fluorescent semiconductor core/shell nanoparticle preferably, nanocrystal
  • a stabilizing copolymer having 1) pendent phosphine, arsine or stibine groups, and 2) pendent fluorochemical groups, that is combined with, attached to, or associated with, the core/shell nanoparticle.
  • the fluorescent semiconductor core/shell nanoparticle includes: an InP core; an inner shell overcoating the core, wherein the inner shell includes zinc selenide and zinc sulfide; and an outer shell overcoating the inner shell, wherein the outer shell includes zinc sulfide.
  • Alkyl means a linear or branched, cyclic or acylic, saturated monovalent hydrocarbon.
  • Alkylene means a linear or branched unsaturated divalent hydrocarbon.
  • Alkenyl means a linear or branched unsaturated hydrocarbon.
  • Aryl means a monovalent aromatic, such as phenyl, naphthyl and the like.
  • Alkylene means a polyvalent, aromatic, such as phenylene, naphthalene, and the like.
  • Alkylene means a group defined above with an aryl group attached to the alkylene, e.g., benzyl, 1-naphthyl ethyl, and the like.
  • heterohydrocarbyl is inclusive of hydrocarbyl alkyl, aryl, aralkyl and alkaryl groups, and heterohydrocarbyl heteroalkyl and heteroaryl groups, the later comprising one or more catenary (in-chain) heteroatoms such as ether or amino groups.
  • Heterohydrocarbyl may optionally contain one or more catenary (in-chain) functional groups including ester, amide, urea, urethane, and carbonate functional groups.
  • the non-polymeric (hetero)hydrocarbyl groups typically contain from 1 to 60 carbon atoms.
  • heterohydrocarbyl s as used herein include, but are not limited to, methoxy, ethoxy, propoxy, 4-diphenylaminobutyl, 2- (2'-phenoxyethoxy)ethyl, 3,6-dioxaheptyl, 3,6-dioxahexyl-6-phenyl, in addition to those described for "alkyl", “heteroalkyl", and “aryl” supra.
  • composite particle refers to a nanoparticle, which is typically in the form of a core/shell nanoparticle (preferably, nanocrystal), having any associated organic coating or other material on the surface of the nanoparticle that is not removed from the surface by ordinary solvation.
  • Such composite particles are useful as "quantum dots,” which have a tunable emission in the near ultraviolet (UV) to far infrared (IR) range as a result of the use of a semiconductor material.
  • nanoparticle refers to a particle having an average particle diameter in the range of 0.1 to 1000 nanometers such as in the range of 0.1 to 100 nanometers or in the range of 1 to 100 nanometers.
  • diameter refers not only to the diameter of substantially spherical particles but also to the distance along the smallest axis of the structure. Suitable techniques for measuring the average particle diameter include, for example, scanning tunneling microscopy, light scattering, and transmission electron microscopy.
  • a “core” of a nanoparticle is understood to mean a nanoparticle (preferably, a nanocrystal) to which no shell has been applied or to the inner portion of a core/shell nanoparticle.
  • a core of a nanoparticle can have a homogenous composition or its composition can vary with depth inside the core.
  • Many materials are known and used in core nanoparticles, and many methods are known in the art for applying one or more shells to a core nanoparticle.
  • the core has a different composition than the one more shells.
  • the core typically has a different chemical composition than the shell of the core/shell nanoparticle.
  • FIG. 1 is a schematic side elevation view of an edge region of an illustrative film article including quantum dots.
  • FIG. 2 is a flow diagram of an illustrative method of forming a quantum dot film.
  • FIG. 3 is a schematic illustration of an embodiment of a display including a quantum dot article.
  • Fig. 4 illustrates the color measurement system.
  • Fig. 5 illustrates the change in quantum yield of InP upon light exposure.
  • the present disclosure provides composite particles that contain fluorescent semiconductor nanoparticles that can fluoresce when excited with actinic radiation.
  • the composite particles can be used in coatings and films for use in optical displays.
  • Fluorescent semiconductor nanoparticles emit a fluorescence signal when suitably excited. They fluoresce at a second wavelength of actinic radiation when excited by a first wavelength of actinic radiation that is shorter than the second wavelength.
  • the fluorescent semiconductor nanoparticles can fluoresce in the visible region of the electromagnetic spectrum when exposed to wavelengths of light in the ultraviolet region of the electromagnetic spectrum. In other embodiments, the fluorescent semiconductor nanoparticles can fluoresce in the infrared region when excited in the ultraviolet or visible regions of the electromagnetic spectrum.
  • the fluorescent semiconductor nanoparticles can fluoresce in the ultraviolet region when excited in the ultraviolet region by a shorter wavelength of light, can fluoresce in the visible region when excited by a shorter wavelength of light in the visible region, or can fluoresce in the infrared region when excited by a shorter wavelength of light in the infrared region.
  • the fluorescent semiconductor nanoparticles are often capable of fluorescing in a wavelength range such as, for example, at a wavelength up to 1200 nanometers (nm), or up to 1000 nm, up to 900 nm, or up to 800 nm.
  • the fluorescent semiconductor nanoparticles are often capable of fluorescence in the range of 400 to 800 nanometers.
  • the nanoparticles have an average particle diameter of at least 0.1 nanometer (nm), or at least 0.5 nm, or at least 1 nm.
  • the nanoparticles have an average particle diameter of up to 1000 nm, or up to 500 nm, or up to 200 nm, or up to 100 nm, or up to 50 nm, or up to 20 nm, or up to 10 nm.
  • Semiconductor nanoparticles, particularly with sizes on the scale of 1-10 nm, have emerged as a category of the most promising advanced materials for cutting-edge technologies.
  • Semiconductor materials include elements or complexes of Group 2-Group 16, Group 12-Group 16, Group 13 -Group 15, Group 14-Group 16, and Group 14
  • quantum dots include a metal phosphide, a metal selenide, a metal telluride, or a metal sulfide.
  • Exemplary semiconductor materials include, but are not limited to, Si, Ge, Sn, BN, BP, BAs, AIN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AIN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, MgTe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO,
  • exemplary metal phosphide quantum dots include indium phosphide and gallium phosphide
  • exemplary metal selenide quantum dots include cadmium selenide, lead selenide, and zinc selenide
  • exemplary metal sulfide quantum dots include cadmium sulfide, lead sulfide, and zinc sulfide
  • exemplary metal telluride quantum dots include cadmium telluride, lead telluride, and zinc telluride.
  • Other suitable quantum dots include gallium arsenide and indium gallium phosphide.
  • Exemplary semiconductor materials are commercially available from Evident Thermoelectrics (Troy, NY), and from Nanosys Inc., Mi!pitas, CA.
  • Nanocrystals (or other nanostructures) for use in the present invention can be produced using any method known to those skilled in the art. Suitable methods are disclosed in U. S. Patent Application No. 10/796,832, filed March 10, 2004, U. S. Patent No. 6,949,206 (Whiteford) and U.S. Provisional Patent Application No. 60/578,236, filed June 8, 2004, the disclosures of each of which are incorporated by reference herein in their entireties.
  • the nanocrystals (or other nanostructures) for use in the present invention can be produced from any suitable material, suitably an inorganic material, and more suitably an inorganic conductive or semiconductive material.
  • Suitable semiconductor materials include those disclosed in U.S. patent application Ser. No. 10/796,832 and include any type of semiconductor, including group 12-16, group 13-15, group 14-16 and group 14 semiconductors.
  • Suitable semiconductor materials include, but are not limited to, Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, A1N, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, A1N, A1P, As, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS,
  • the semiconductor nanocrystals or other nanostructures may comprise a dopant from the group consisting of: a p-type dopant or an n-type dopant.
  • the nanocrystals (or other nanostructures) useful in the present invention can also comprise Group 12-Group 16 or Group 13 -Group 15 semiconductors.
  • Group 12- Group 16 or Group 13-Group 15 semiconductor nanocrystals and nanostructures include any combination of an element from Group 12, such as Zn, Cd and Hg, with any element from Group 16, such as S, Se, Te, Po, of the Periodic Table; and any combination of an element from Group 13, such as B, Al, Ga, In, and Tl, with any element from Group 15, such as N, P, As, Sb and Bi, of the Periodic Table.
  • Suitable inorganic nanostructures include metal nanostructures.
  • Suitable metals include, but are not limited to, Ru, Pd, Pt, Ni, W, Ta, Co, Mo, Ir, Re, Rh, Hf, Nb, Au, Ag, Ti, Sn, Zn, Fe, FePt, and the like.
  • metal precursors that undergo pyrolysis at high temperature are rapidly injected into a hot solution of organic surfactant molecules. These precursors break apart at elevated temperatures and react to nucleate nanocrystals. After this initial nucleation phase, a growth phase begins by the addition of monomers to the growing crystal. The result is freestanding crystalline nanoparticles in solution that have an organic surfactant molecule coating their surface.
  • synthesis occurs as an initial nucleation event that takes place over seconds, followed by crystal growth at elevated temperature for several minutes.
  • Parameters such as the temperature, types of surfactants present, precursor materials, and ratios of surfactants to monomers can be modified so as to change the nature and progress of the reaction.
  • the temperature controls the structural phase of the nucleation event, rate of decomposition of precursors, and rate of growth.
  • the organic surfactant molecules mediate both solubility and control of the nanocrystal shape.
  • Core-shell structures are obtained by adding organometallic precursors containing the shell materials to a reaction mixture containing the core nanocrystal.
  • the cores act as the nuclei, and the shells grow from their surface.
  • the temperature of the reaction is kept low to favor the addition of shell material monomers to the core surface, while preventing independent nucleation of nanocrystals of the shell materials.
  • Surfactants in the reaction mixture are present to direct the controlled growth of shell material and ensure solubility.
  • a uniform and epitaxially grown shell is obtained when there is a low lattice mismatch between the two materials.
  • the spherical shape acts to minimize interfacial strain energy from the large radius of curvature, thereby preventing the formation of dislocations that could degrade the optical properties of the nanocrystal system.
  • ZnS can be used as the shell material using known synthetic processes, resulting in a high-quality emission. As above, if necessary, this material can be easily substituted, e.g., if the core material is modified. Additional exemplary core and shell materials are described herein and/or known in the art.
  • the first factor is the ability to absorb and emit visible light. This consideration makes InP a highly desirable base material.
  • the second factor is the material's photoluminescence efficiency (quantum yield).
  • Quantum yield Generally, Group 12-16 quantum dots (such as cadmium selenide) have higher quantum yield than Group 13-15 quantum dots (such as InP).
  • the quantum yield of InP cores produced previously has been very low ( ⁇ 1 %), and therefore the production of a core/shell structure with InP as the core and another semiconductor compound with higher bandgap (e.g., ZnS) as the shell has been pursued in attempts to improve the quantum yield.
  • the fluorescent semiconductor nanoparticles i.e., quantum dots
  • the fluorescent semiconductor nanoparticles include a core and a shell at least partially surrounding the core.
  • the core/shell nanoparticles can have two distinct layers, a semiconductor or metallic core and a shell surrounding the core of an insulating or semiconductor material.
  • the core often contains a first semiconductor material and the shell often contains a second
  • a first Group 12-16 (e.g., CdSe) semiconductor material can be present in the core and a second Group 12-16 (e.g., ZnS) semiconductor material can be present in the shell.
  • a first Group 12-16 e.g., CdSe
  • a second Group 12-16 e.g., ZnS
  • the core includes a metal phosphide (e.g., indium phosphide (InP), gallium phosphide (GaP), aluminum phosphide (A1P)), a metal selenide (e.g., cadmium selenide (CdSe), zinc selenide (ZnSe), magnesium selenide (MgSe)), or a metal telluride (e.g., cadmium telluride (CdTe), zinc telluride (ZnTe)).
  • the core includes a metal phosphide (e.g., indium phosphide) or a metal selenide (e.g., cadmium selenide).
  • a metal phosphide e.g., indium phosphide
  • a metal selenide e.g., cadmium selenide
  • the core includes a metal phosphide (e.g., indium phosphide).
  • a metal phosphide e.g., indium phosphide
  • the shell can be a single layer or multilayered. In some embodiments, the shell is a multilayered shell.
  • the shell can include any of the core materials described herein.
  • the shell material can be a semiconductor material having a higher bandgap energy than the semiconductor core.
  • suitable shell materials can have good conduction and valence band offset with respect to the semiconductor core, and in some embodiments, the conduction band can be higher and the valence band can be lower than those of the core.
  • semiconductor cores that emit energy in the visible region such as, for example, CdS, CdSe, CdTe, ZnSe, ZnTe, GaP, InP, or GaAs
  • near IR region such as, for example, InP, InAs, InSb, PbS, or PbSe
  • semiconductor cores that emit in the near IR region can be coated with a material having a bandgap energy in the visible region such as CdS or ZnSe.
  • Suitable core and shell precursors useful for preparing semiconductor cores are known in the art and can include Group 2 elements, Group 12 elements, Group 13 elements, Group 14 elements, Group 15 elements, Group 16 elements, and salt forms thereof.
  • a first precursor may include metal salt (M+X-) including a metal atom (M+) such as, for example, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Ga, In, Al, Pb, Ge, Si, or in salts and a counter ion (X-), or organometallic species such as, for example, dialkyl metal complexes.
  • the shell includes a metal sulfide (e.g., zinc sulfide or cadmium sulfide).
  • the shell includes a zinc-containing compound (e.g., zinc sulfide or zinc selenide).
  • a multilayered shell includes an inner shell overcoating the core, wherein the inner shell includes zinc selenide and zinc sulfide.
  • a multilayered shell includes an outer shell overcoating the inner shell, wherein the outer shell includes zinc sulfide.
  • the core of the shell/core nanoparticle contains a metal phosphide such as indium phosphide, gallium phosphide, or aluminum phosphide.
  • the shell contains zinc sulfide, zinc selenide, or a combination thereof.
  • the core contains indium phosphide and the shell is multilayered with the inner shell containing both zinc selenide and zinc sulfide and the outer shell containing zinc sulfide.
  • the thickness of the shell(s) may vary among embodiments and can affect fluorescence wavelength, quantum yield, fluorescence stability, and other photostability characteristics of the nanocrystal. The skilled artisan can select the appropriate thickness to achieve desired properties and may modify the method of making the core/shell nanoparticles to achieve the appropriate thickness of the shell(s).
  • the diameter of the fluorescent semiconductor nanoparticles (i.e., quantum dots) of the present disclosure can affect the fluorescence wavelength.
  • the diameter of the quantum dot is often directly related to the fluorescence wavelength. For example, cadmium selenide quantum dots having an average particle diameter of about 2 to 3 nanometers tend to fluoresce in the blue or green regions of the visible spectrum while cadmium selenide quantum dots having an average particle diameter of about 8 to 10 nanometers tend to fluoresce in the red region of the visible spectrum.
  • InP may be purified by bonding with dodecylsuccinic acid (DDSA) and lauric acid (LA) first, following by precipitation from ethanol, the precipitated quantum dots may have some of the acid functional ligands attached thereto, prior to dispersing in the fluid carrier.
  • CdSe quantum dots may be functionalized with amine- functional ligands as result of their preparation, prior to functionalization with the instant ligands.
  • the quantum dots may be functionalized with those surface modifying additives or ligands resulting from the original synthesis of the nanoparticles.
  • the quantum dots may be surface modified with ligands of Formula III: R 5 -R 12 (X)n III
  • R 5 is (hetero)hydrocarbyl group having C2 to C30 carbon atoms
  • R 12 is a hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene;
  • n is at least one
  • X is a ligand group, including -CO2H, -SO3H, -P(0)(OH) 2 , -OP(0)(OH), -OH and - H2.
  • the nanoparticles may be surface modified with fluorochemical ligands of the formula:
  • Rf 1 is a perfluoroalkyl, perfluoroether or perfluoropolyether group of valence w,
  • R 22 is a divalent hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene
  • R 23 is a divalent hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene
  • X 21 is -CH2-O-, -0-, -S-, -CO2-, -CO R 1 -, or -SO2 R 1 - where R 1 is H or C1-C4 alkyl;
  • X 22 is a covalent bond, -S-, -O- or - R 1 -, -CO2-, -CONR 1 -, or -SO2NR 1 - where R 1 is H or C1-C4 alkyl;
  • w 1 or 2;
  • L is an ligand group selected from -CO2H, -SH, -P(0)(OH) 2 , -P(0)OH, -NH2 -OH, and - SO3H.
  • fluorochemical ligands are described in Applicant's copending application US 62/269711, filed 18 December 2015 and incorporated herein by reference.
  • the nanoparticles are ligand functionalized with the compounds of Formula IV to improve the compatibility of the phases.
  • Such additional surface modifying ligands may be added when the functionalizing with the stabilizing copolymer (as described herein and of Formula V), or may be attached to the nanoparticles as result of the synthesis.
  • Such additional surface modifying agents are present in amounts less than or equal to the weight of the instant stabilizing copolymer, preferably 10wt.% or less, relative to the amount of the stabilizing copolymer.
  • Various methods can be used to surface modify the fluorescent semiconductor nanoparticles with the ligand compounds.
  • procedures similar to those described in U.S. 7160613 (Bawendi et al.) and 8,283,412 (Liu et al.) can be used to add the surface modifying agent.
  • the ligand compound and the fluorescent semiconductor nanoparticles can be heated at an elevated temperature (e.g., at least 50°C, at least 60°C, at least 80°C, or at least 90°C) for an extended period of time (e.g., at least 1 hour, at least 5 hours, at least 10 hours, at least 15 hours, or at least 20 hours).
  • any by-product of the synthesis process or any solvent used in surface- modification process can be removed, for example, by distillation, rotary evaporation, or by precipitation of the nanoparticles and centrifugation of the mixture followed by decanting the liquid and leaving behind the surface-modified nanoparticles.
  • the surface-modified fluorescent semiconductor nanoparticles are dried to a powder after surface-modification.
  • the solvent used for the surface modification is compatible (i.e., miscible) with any carrier fluids used in compositions in which the nanoparticles are included.
  • at least a portion of the solvent used for the surface-modification reaction can be included in the carrier fluid in which the surface-modified, fluorescent semiconductor nanoparticles are dispersed.
  • the fluorescent semiconductor nanoparticles are stabilized using a copolymer having 1) pendent phosphine, stibine or arsine groups and 2) pendent fluorochemical groups.
  • the stabilizing copolymer improves the stability of the quantum dots for their use in quantum dot articles.
  • the instant stabilizing copolymer renders the quantum dots stable in the dispersion of fluorochemical carrier fluids, droplets of which are dispersed in the polymeric matrix.
  • the combination of the stabilizing copolymers with the quantum dots may prevent the quantum dot particles from photodegradation.
  • the stabilizing copolymer is of the formula:
  • [M stab ] represents monomer units having pendent phosphine, arsine or stibine groups and subscript d parts by weight;
  • [M FC ] represents fluorochemical -functional monomer units having subscript e parts by weight.
  • the copolymer generally is at least 50, preferably >60, more preferably greater than
  • the number of monomer units of the copolymer is > 8. With reference to Formula V subscripts a+b > 8. It is further preferred that the number of monomer units in the copolymer is ⁇ 30, preferably ⁇ 25.
  • the molecular weight of the copolymer may be controlled by the addition of chain transfer agents during free radical polymerization of the monomers, as is known in the art.
  • a chain transfer agent may also be used during synthesis of the copolymer to control the molecular weight.
  • Chain transfer agents which may be used are mercapto compounds such as dodecylmercaptan, and halogen compounds such as carbon
  • copolymeric copolymers illustrated herein do not show the residue of the chain transfer agent.
  • the monomer units represented by M stab may derived from monomers of the formula:
  • each R 1 is a hydrocarbyl group including alkyl, aryl, alkaryl and aralkyl;
  • R 2 is a divalent hydrocarbyl group selected from alkylene, arylene, alkarylene and aralkylene;
  • Z is P, As or Sb
  • Q 1 is a functional group selected from -CO2-, -0-, -S-, -CONR 3 -, - H-CO- R 3 -, and - R 3 - , where R 3 is H or C1-C4 alkyl, and subscript x is 0 or 1, and
  • R 6 is a divalent hydrocarbyl group selected from alkylene, arylene, alkarylene and aralkylene.
  • R 1 groups is an aryl group, and all of the R 1 groups are aryl groups.
  • R 2 comprises are aryl group, an alkaryl group or an aralkyl group.
  • the copolymer further comprises monomer units derived from monomers of the formula:
  • Q 2 is selected from a covalent bond ("-"), -CO2-, -CO R 3 -, - H-CO- R 3 -, and - R 3 -, where R 3 is H or C1-C4 alkyl;
  • Q 3 is selected from -CH2-S-, -CH2-O-, -CO2-, -CONR 3 -, -NH-CO-NR 3 -, and -NR 3 , where R 3 is H or C1-C4 alkyl,
  • subscripts g and h are independently 0 or 1 ;
  • R 10 is a hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene and Rf is a perfluorinated group.
  • the perfluorinated Rf group may be a perfluoroalkyl, a perfluoroether, or a perfluoropoly ether.
  • the Rf groups can be linear, branched and are of the formula:
  • a is at least 1, preferably 1-10, more preferably 2-6;
  • b is at least 1, preferably 1-10, more preferably 2-6, and c may be a number from 0 to 50, preferably 1 to 30, more preferably 1 to 10.
  • the Rf group is a perfluoroalkyl, and a perfluoroether or perfluoropoly ether when subscript c is non-zero.
  • the Rf has at least one catenated (in-chain) oxygen heteroatoms, i.e. Rf is a perfluoroether or perfluoropolyether.
  • Exemplary perfluoropolyethers include, but are not limited to, those that have perfluorinated repeating units selected from the group of -(C P F2 P )-, -(C P F2 P 0)-, -(CF(Rf 2 ))-, -(CF(Rf 2 )C P F 2p O)-, -(C P F 2p CF(Rf 2 )0)-, -(CF 2 CF(Rf 2 )0)-, or combinations thereof.
  • p is typically an integer of 1 to 10.
  • p is an integer of 1 to 8, 1 to 6, 1 to 4, 1 to 3, or 1 to 2.
  • the group Rf 2 is a fluorine atom, perfluoroalkyl group, perfluoroether group, nitrogen-containing
  • perfluoroalkyl group perfluoropolyether, or a perfluoroalkoxy group, all of which can be linear, branched, or cyclic.
  • the Rf 2 group typically has no more than 12 carbon atoms, no more than 10 carbon atoms, or no more than 9 carbon atoms, no more than 4 carbon atoms, no more than 3 carbon atoms, no more than 2 carbon atoms, or no more than 1 carbon atom.
  • the Rf 2 group can have no more than 4, no more than 3, no more than 2, no more than 1, or no oxygen atoms.
  • the different repeat units can be distributed randomly along the chain.
  • Rf groups include, but are not limited to, Rf'-CF20(CF 2 0) q (C2F40)rCF2-, Rf'-(CF 2 )30(C4F 8 0)r(CF2) 3-, Rf' -CF20(C2F 4 0)rCF2-, and
  • r has an average value of 0 to 50, 3 to 30, 3 to 15, or 3 to 10
  • s has an average value of 0 to 50, 1 to 50, 3 to 30, 3 to 15, or 3 to 10
  • the sum (r + s) has an average value of 1 to 50 or 4 to 40
  • the sum (q + r) is greater than 0
  • t is an integer of 2 to 6.
  • compounds typically include a mixture of Rf groups.
  • the average structure is the structure averaged over the mixture components.
  • the values of q, r, and s in these average structures can vary, as long as the compound has a number average molecular weight of at least about 300.
  • Useful compounds often have a molecular weight
  • Rf is the oligomer of hexafluoropropylene oxide (FIFPO) with a number average molecular weight at least 1,000.
  • FPO hexafluoropropylene oxide
  • the ligands may be prepared from a perfluoroether ester, such as
  • the ester can be reacted with a hydroxy amine followed by further functionalization to provide the polymerizable group:
  • An ester of a perfluorinated acid can be reduced to a -CH2-OH group, facilitating preparation of compounds having a -CH2-OH "Q 3 " group.
  • This in turn may be reacted with a vinyl halide, such as allyl bromide to provide a terminal allyl unsaturation.
  • nucleophilic -CH2-OH terminal group with a compound having an electrophilic group to provide the requisite unsaturation.
  • Rf-CH 2 -OH + VII where E is an electrophilic functional group including ester, acid halide, isocyanate, aziridine, and other known in the art.
  • the -CH2-O- "Q 3 " group can be converted to a -CH2-S- group by reacting with a perfluorosulfonyl fluoride, displacement with a thioester, followed by hydrolysis.
  • -CH2-SH may be used in displacement and condensation reaction, or in ene reactions to provide the requisite unsaturation.
  • Longer chain thiols may be prepared by reacting compounds of the formula Rf-CFhOH with an allyl halide to provide a terminal allyl group, followed by an ene reaction with a thioester, and hydrolysis.
  • R f -CH 2 OH Rf-CH 2 OS0 2 -C 4 F 9
  • R f -CH 2 OCH2-CH CH2 ⁇ Rf-CH 2 CH 2 CH 2 -S-CO-CH 3 ⁇ Rf-CH 2 CH 2 CH 2 -SH
  • a perfluorinated acid fluoride may be reacted with fluoride ion to produce an intermediate having a nucleophilic -CF 2 -0 " group as shown.
  • perfluoroketones may be reacted with fluoride ion to produce a secondary
  • a dispersion of the copolymer stabilized nanoparticles composition may also include a fluorinated carrier fluid.
  • the dispersion comprises a fluorinated carrier fluid.
  • the fluorinated carrier fluid are typically selected to be compatible (i.e., miscible) with the stabilizing copolymer added to the fluorescent semiconductor nanoparticles.
  • the copolymer stabilized nanoparticles and fluorinated carrier fluid form a coating that is transparent when viewed with the human eye.
  • any precursors of the polymeric materials that are included in the dispersion composition are soluble in a fluorinated carrier fluid and form a coating that is transparent when viewed with the unaided human eye.
  • the term transparent means transmitting at least 85% of incident light in the visible spectrum (about 400-700 nm wavelength).
  • the optional fluorinated carrier fluids are inert, liquid at 25°C and have a boiling point >100°C, preferably >150°C; and can be one or a mixture of perfluorinated or highly fluorinated liquid compounds having, in some embodiments, at least 8 carbon atoms or more, and optionally containing one or more catenary heteroatoms, such as divalent oxygen, hexavalent sulfur, or trivalent nitrogen and having a hydrogen content of less than 5 percent by weight or less than 1 percent by weight. Higher boiling points are preferred so that the carrier fluids remain when organic solvents used in the preparation are removed.
  • Suitable fluorinated, inert fluids useful of the present disclosure include, for example, perfluoroalkanes or perfluorocycloalkanes, such as, perfluorooctane,
  • perfluorodecalin perfluoromethyldecalin
  • perfluoroamines such as, perfluorotripentyl amine, perfluorotributyl amine, perfluorotripropyl amine, perfluorotriamyl amine, and perfluoro-N-isopropyl mo holine
  • perfluoroethers such as
  • the copolymer stabilized quantum dots are added to the fluid carrier in amounts such that the optical density is at least 10, optical density defined as the absorbance at 440nm for a cell with a path length of 1 cm solution.
  • the stabilized fluorescent semiconductor nanoparticles may be dispersed in a solution, suspension or dispersion that contains (a) a fluorinated carrier fluid and (b) a polymeric binder, a precursor of the polymeric binder, or combinations thereof.
  • the ligand functionalized nanoparticles may be dispersed in the carrier fluid, which is then dispersed in the polymeric binder, forming droplets of the nanoparticles in the carrier, fluid, which in turn are dispersed in the polymeric binder.
  • the nanoparticles may be surface-modified by the fluorochemical ligands of Formula V.
  • the polymeric binders desirably provide barrier properties to exclude oxygen and moisture. If water and/or oxygen enter the quantum dot article, the quantum dots can degrade and ultimately fail to emit light when excited by ultraviolet or blue light irradiation. Slowing or eliminating quantum dot degradation along the laminate edges is particularly important to extend the service life of the displays in smaller electronic devices such as those utilized in, for example, handheld devices and tablets.
  • the polymeric binders or resins desirably provide barrier properties to exclude oxygen and moisture when cured. If water and/or oxygen enter the quantum dot article, the quantum dots can degrade and ultimately fail to emit light when excited by ultraviolet or blue light irradiation. Slowing or eliminating quantum dot degradation along the laminate edges is particularly important to extend the service life of the displays in smaller electronic devices such as those utilized in, for example, handheld devices and tablets.
  • Exemplary polymeric binders include, but are not limited to, polysiloxanes, fluoroelastomers, polyamides, polyimides, polycarolactones, polycaprolactams, polyurethanes, polyethers, polyvinyl chlorides, polyvinyl acetates, polyesters,
  • polycarbonates polyacrylates, polymethacrylates, polyacrylamides, and
  • Suitable precursors of the polymeric binder or resin include any precursor materials used to prepare the polymeric materials listed above.
  • Exemplary precursor materials include acrylates that can be polymerized to polyacrylates, methacrylates that can be polymerized to form polymethacrylates, acrylamides that can be polymerized to form polyacrylamides, methacrylamides that can be polymerized to form
  • polymethacrylamides epoxy resins and dicarboxylic acids that can be polymerized to form polyesters
  • diepoxides that can be polymerized to form polyethers
  • isocyanates and polyols that can be polymerized to form polyurethanes
  • polyols and dicarboxylic acids that can be polymerized to form polyesters.
  • the polymeric binder is a thermally curable epoxy-amine composition optionally further comprising a radiation-curable acrylate as described in Applicant's copending WO 2015095296 (Eckert et al.); Thiol-epoxy resins as described in US 62/148219 (Qiu et al., filed 16 April 2015), thiol-alkene-epoxy resins as described in US 62148212 (Qui et al. filed 16 April 2015); thiol-alkene resins as described in US 62/080488 (Qui et al., filed 17 November 2014), and thiol silicones as described in
  • ROUg groups include urethanes, polyurethanes, esters, polyesters, polyethers, polyolefins, polybutadienes and epoxies;
  • L 1 is a linking group
  • Z 1 is a pendent, free-radically polymerizable group such as (meth)acryloyl, vinyl or alkynyl and is preferably a (meth)acrylate, and
  • the linking group L 1 between the oligomer segment and ethylenically unsaturated end group includes a divalent or higher valency group selected from an alkylene, arylene, heteroalkylene, or combinations thereof and an optional divalent group selected from carbonyl, ester, amide, sulfonamide, or combinations thereof.
  • L 1 can be unsubstituted or substituted with an alkyl, aryl, halo, or combinations thereof.
  • the L 1 group typically has no more than 30 carbon atoms. In some compounds, the L 1 group has no more than 20 carbon atoms, no more than 10 carbon atoms, no more than 6 carbon atoms, or no more than 4 carbon atoms.
  • L 1 can be an alkylene, an alkylene substituted with an aryl group, or an alkylene in combination with an arylene or an alkyl ether or alkyl thioether linking group.
  • the pendent, free radically polymerizable functional groups Z 1 may be selected from the group consisting of vinyl, vinyl ether, ethynyl, and (meth)acyroyl which includes acrylate, methacrylate, acrylamide and methacryl amide groups.
  • the oligomeric group R ollg may be selected from poly(meth)acrylate, polyurethane, poly epoxide, polyester, poly ether, polysulfide, polybutadiene, hydrogenated poly olefins (including hydrogenated polybutadienes, isoprenes and ethylene/propylene copolymers, and polycarbonate oligomeric chains.
  • (meth)acrylated oligomer means a polymer molecule having at least two pendent (meth)acryloyl groups and a weight average molecular weight (M w ) as determined by Gel Permeation Chromatography of at least 1,000 g/mole and typically less than 50,000 g/mole.
  • (Meth)acryloyl epoxy oligomers are multifunctional (meth)acrylate esters and amides of epoxy resins, such as the (meth)acrylated esters of bisphenol-A epoxy resin.
  • Examples of commercially available (meth)acrylated epoxies include those known by the trade designations EBECRYL 600 (bisphenol A epoxy diacrylate of 525 molecular weight), EBECRYL 605 (EBECRYL 600 with 25% tripropylene glycol diacrylate), EBECRYL 3700 (bisphenol-A diacrylate of 524 molecular weight) and EBECRYL 3720H (bisphenol A diacrylate of 524 molecular weight with 20% hexanediol diacrylate) available from Cytec Industries, Inc., Woodland Park, NJ; and PHOTOMER 3016 (bisphenol A epoxy acrylate), PHOTOMER 3016-40R (epoxy acrylate and 40% tripropylene glycol diacrylate blend), and PHOTOMER 3072 (mod
  • (Meth)acrylated urethanes are multifunctional (meth)acrylate esters of hydroxy terminated isocyanate extended polyols, polyesters or polyethers.
  • (Meth)acrylated urethane oligomers can be synthesized, for example, by reacting a diisocyanate or other polyvalent isocyanate compound with a polyvalent polyol (including polyether and polyester polyols) to yield an isocyanate terminated urethane prepolymer.
  • a polyester polyol can be formed by reacting a polybasic acid (e.g., terephthalic acid or maleic acid) with a polyhydric alcohol (e.g., ethylene glycol or 1,6-hexanediol).
  • a polyether polyol useful for making the acrylate functionalized urethane oligomer can be chosen from, for example, polyethylene glycol, polypropylene glycol, poly(tetrahydrofuran), poly(2- methyl-tetrahydrofuran), poly(3-methyl-tetrahydrofuran) and the like.
  • the polyol linkage of an acrylated urethane oligomer can be a polycarbonate polyol.
  • (meth)acrylates having a hydroxyl group can then be reacted with the terminal isocyanate groups of the prepolymer.
  • Both aromatic and the preferred aliphatic isocyanates can be used to react with the urethane to obtain the oligomer.
  • diisocyanates useful for making the (meth)acrylated oligomers are 2,4- tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate and the like.
  • hydroxy terminated acrylates useful for making the acrylated oligomers include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, a- hydroxybutyl acrylate, polyethylene glycol (meth)acrylate and the like.
  • a (meth)acrylated urethane oligomer can be, for example, any urethane oligomer having at least two acrylate functionalities and generally less than about six functionalities.
  • Suitable (meth)acrylated urethane oligomers are also commercially available such as, for example, those known by the trade designations PHOTOMER 6008, 6019, 6184 (aliphatic urethane triacrylates) available from Henkel Corp.; EBECRYL 220 (hexafunctional aromatic urethane acrylate of 1000 molecular weight), EBECRYL 284 (aliphatic urethane diacrylate of 1200 molecular weight diluted with 12% of 1 ,6- hexanediol diacrylate), EBECRYL 4830 (aliphatic urethane diacrylate of 1200 molecular weight diluted with 10% of tetraethylene glycol diacrylate), and EBECRYL 6602 (trifunctional aromatic urethane acrylate of 1
  • Diisocyanates are widely used in urethane acrylate synthesis and can be divided into aromatic and aliphatic diisocyanates.
  • Aromatic diisocyanates are used for manufacture of aromatic urethane acrylates which have significantly lower cost than aliphatic urethane acrylates but tend to noticeably yellow on white or light colored substrates.
  • Aliphatic urethane acrylates include aliphatic diisocyanates that exhibit slightly more flexibility than aromatic urethane acrylates that include the same functionality, a similar polyol modifier and at similar molecular weight.
  • the curable composition may comprise a functionalized poly(meth)acrylate oligomer, which may be obtained from the reaction product of: (a) from 50 to 99 parts by weight of (meth)acrylate ester monomer units that are homo- or co-polymerizable to a polymer (b) from 1 to 50 parts by weight of monomer units having a pendent, free- radically polymerizable functional group.
  • a functionalized poly(meth)acrylate oligomer which may be obtained from the reaction product of: (a) from 50 to 99 parts by weight of (meth)acrylate ester monomer units that are homo- or co-polymerizable to a polymer (b) from 1 to 50 parts by weight of monomer units having a pendent, free- radically polymerizable functional group.
  • Examples of such materials are available from Lucite International (Cordova, TN) under the trade designations of Elvacite 1010, Elvacite 4026, and Elvacite 4059.
  • the (meth)acrylated poly(meth)acrylate oligomer may comprise a blend of an acrylic or hydrocarbon polymer with multifunctional (meth)acrylate diluents.
  • Suitable polymer/diluent blends include, for example, commercially available products such as EBECRYL 303, 745 and 1710 all of which are available from Cytec Industries, Inc., Woodland Park, NJ.
  • the curable composition may comprise a (meth)acrylated polybutadiene oligomer, which may be obtained from a carboxyl- or hydroxyl- functionalized polybutadiene.
  • carboxyl or hydroxy functionalised polybutadiene is meant to designate a polybutadiene comprising free -OH or— COOH groups.
  • Carboxyl functionalized polybutadienes are known, they have for example been described in U.S. 3,705,208 (Nakamuta et al.) and are commercially available under the trade name of Nisso PB C-1000 (Nisso America, New York, NY).
  • Carboxyl functionalized polybutadienes can also be obtained by the reaction of a hydroxyl functionalized polybutadiene (that is a polybutadiene having free hydroxyl groups) with a cyclic anhydride such as for example has been described in U.S. 5,587,433 (Boeckeler), U.S. 4,857,434 (Klinger) and U.S. 5,462,835 (Mirle).
  • a hydroxyl functionalized polybutadiene that is a polybutadiene having free hydroxyl groups
  • a cyclic anhydride such as for example has been described in U.S. 5,587,433 (Boeckeler), U.S. 4,857,434 (Klinger) and U.S. 5,462,835 (Mirle).
  • Carboxyl and hydroxyl functionalized polybutadienes suitable for being used in the process according to the present invention contain besides the carboxyl and/or hydroxyl groups, units derived from the polymerization of butadiene.
  • the number average molecular weight (M n ) of the functionalized polybutadiene is preferably from 200 to 10000 Da.
  • the M n is more preferably at least 1000.
  • the Mn more preferably does not exceed 5000 Da.
  • The— COOH or -OH functionality is generally from 1.5 to 9, preferably from 1.8 to 6.
  • this cyclic anhydride preferably include phthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride, succinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride. Mixtures of anhydrides can also be used.
  • the amount of anhydride used for the preparation of a carboxyl functionalized polybutadiene from a hydroxyl functionalized polybutadiene is generally at least 0.8 molar, preferably at least 0.9 molar and more preferably at least 0.95 molar equivalent per molar equivalents of— OH groups present in the polybutadiene.
  • a (meth)acrylated polybutadiene oligomer which is the reaction product of a carboxyl functionalized polybutadiene, may be prepared with a (meth)acrylated monoepoxide.
  • (Meth)acrylated mono-epoxides are known. Examples of (meth)acrylated mono-epoxides that can be used are glycidyl (meth)acrylate esters, such as
  • glycidylacrylate glycidylmethacrylate, 4-hydroxybutylacrylate glycidylether, bisphenol-A diglycidylether monoacrylate.
  • the (meth)acrylated mono-epoxides are preferably chosen from glycidylacrylate and glycidylmethacrylate.
  • a (meth)acrylated polybutadiene oligomer which is the reaction product of a hydroxyl functionalized polybutadiene may be prepared with a (meth)acrylate ester, or halide.
  • Some (meth)acrylated polybutadienes that can be used, for example, include
  • Ricacryl 3100 and Ricacryl 3500 manufactured by Sartomer Company, Exton, PA., USA, and Nisso TE-2000 available from Nisso America, New York, NY.
  • other methacrylated polybutadienes can be used. These include dimethacrylates of liquid polybutadiene resins composed of modified, esterified liquid polybutadiene diols. These are available under the tradename CN301 and CN303, and CN307, manufactured by
  • the methacrylated polybutadiene can include a number of methacrylate groups per chain from about 2 to about 20.
  • the acrylate functionalized oligomers can be polyester acrylate oligomers, acrylated acrylic oligomers, acrylated epoxy oligomers, polycarbonate acrylate oligomers or polyether acrylate oligomers.
  • Useful epoxy acrylate oligomers include CN2003B from Sartomer Co. (Exton, PA).
  • Useful polyester acrylate oligomers include CN293, CN294, and CN2250, 2281, 2900 from Sartomer Co. (Exton, PA) and EBECRYL 80, 657, 830, and 1810 from UCB Chemicals (Smyrna, GA).
  • Suitable polyether acrylate oligomers include CN501, 502, and 551 from Sartomer Co. (Exton, PA).
  • Useful polycarbonate acrylate oligomers can be prepared according to U.S. 6,451,958 (Sartomer Technology Company Inc., Wilmington, DE).
  • the curable binder composition optionally, yet preferably, comprises diluent monomer in an amount sufficient to reduce the viscosity of the curable composition such that it may be coated on a substrate.
  • the composition may comprise up to about 70 wt-% diluent monomers to reduce the viscosity of the oligomeric component to less than 10000 centipoise and to improve the processability.
  • Useful monomers are desirably soluble or miscible in the (meth)acrylated oligomer, highly polymerizable therewith.
  • Useful diluents are mono- and
  • polyethylenically unsaturated monomers such as (meth)acrylates or (meth)acrylamides.
  • Suitable monomers typically have a number average molecular weight no greater than 450 g/mole.
  • the diluent monomer desirably has minimal absorbance at the wavelength of the radiation used to cure the composition.
  • Such diluent monomers may include, for example, n-butyl aciylate, isobutyl aciylate, hexyl aciylate, 2-ethyl-hexylacrylate, isooctylacrylate, caprolactoneacrylate, isodecylacrylate, tridecylacrylate, lauiylmethacrylate, methoxy- polyethylenglycol-monomethacrylate, laurylacrylate, tetrahydrofurfuryl-acrylate, ethoxy- ethoxyethyl aciylate and ethoxy lated-nonyl aciylate.
  • N-vinylpyrrolidone N-vinyl caprolactam
  • isobornyl aciylate acryloylmorpholine
  • isobornylmethacrylate phenoxyethylacrylate
  • phenoxyethylmethacrylate methylmethacrylate and acrylamide.
  • the diluent monomers may contain an average of two or more free- radically polymerizable groups.
  • a diluent having three or more of such reactive groups can be present as well. Examples of such monomers include: C2-C18
  • alkylenedioldi(meth)acrylates C3-C18 alkylenetrioltri(meth)acrylates, the polyether analogues thereof, and the like, such as l,6-hexanedioldi(meth)acrylate,
  • Suitable preferred diluent monomers include for example benzyl (meth)acrylate, phenoxyethyl (meth)acrylate; phenoxy-2-methylethyl (meth)acrylate; phenoxyethoxyethyl (meth)acrylate, 1-naphthyloxy ethyl aciylate; 2-naphthyloxy ethyl aciylate; phenoxy 2- methylethyl aciylate; phenoxyethoxyethyl aciylate; 2-phenylphenoxy ethyl aciylate; 4- phenylphenoxy ethyl aciylate; and phenyl aciylate .
  • Preferred diluent monomers includes phenoxyethyl (meth)acrylate, benzyl
  • (meth)acrylate, and tricyclodecane dimethanol diacrylate Phenoxyethyl aciylate is commercially available from Sartomer under the trade designation "SR339"; from Eternal Chemical Co. Ltd. under the trade designation “Etermer 210"; and from Toagosei Co. Ltd under the trade designation "TO- 1166". Benzyl aciylate is commercially available from Osaka Organic Chemical, Osaka City, Japan. Tricyclodecane dimethanol diacrylate is commercially available from Sartomer under the trade designation "SR833".
  • Such optional monomer(s) may be present in the polymerizable composition in amount of at least about 5 wt-%. The optional monomer(s) typically total no more than about 70 wt-% of the curable composition. The some embodiments the total amount of diluent monomer ranges from about 10 wt-% to about 50-%.
  • the curable composition When using a free-radically curable polymeric binder, the curable composition further comprises photoinitiators, in an amount between the range of about 0.1% and about 5% by weight.
  • Photoinitiators include those known as useful for photocuring free-radically polyfunctional (meth)acrylates.
  • exemplary photoinitiators include benzoin and its derivatives such as alpha-methylbenzoin; alpha-phenylbenzoin; alpha-allylbenzoin; alpha- benzylbenzoin; benzoin ethers such as benzil dimethyl ketal (e.g., "IRGACURE 651 " from BASF, Florham Park, NJ), benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether; acetophenone and its derivatives such as 2-hydroxy-2-methyl-l -phenyl- 1-propanone (e.g., "DAROCUR 1173" from BASF, Florham Park, NJ) and 1 -hydroxy cyclohexyl phenyl ketone (e.g., "IRGACURE 184" from BASF, Florham Park, NJ); 2-methyl-l-[4
  • photoinitiators include, for example, pivaloin ethyl ether, anisoin ethyl ether, anthraquinones (e.g., anthraquinone, 2-ethylanthraquinone, 1- chloroanthraquinone, 1,4-dimethylanthraquinone, 1-methoxyanthraquinone, or
  • benzanthraquinone halomethyltriazines
  • benzophenone and its derivatives iodonium salts and sulfonium salts
  • titanium complexes such as bis(eta5-2,4-cyclopentadien-l-yl)- bis[2,6-difluoro-3-(lH-pyrrol-l-yl) phenyl ]titanium (e.g., "CGI 784DC” from BASF, Florham Park, NJ); halomethyl-nitrobenzenes (e.g., 4-bromomethylnitrobenzene), mono- and bis-acylphosphines (e.g., "IRGACURE 1700", “IRGACURE 1800", “IRGACURE 1850", and "DAROCUR 4265").
  • the polymeric binder is an epoxy compound that can be cured or polymerized by the processes that are those known to undergo cationic polymerization and include 1,2-, 1,3-, and 1,4-cyclic ethers (also designated as 1,2-, 1,3-, and 1,4-epoxides).
  • Suitable epoxy binders can include, for example, those epoxy binders described in U.S. Patent No. 6,777,460.
  • cyclic ethers that are useful include the cycloaliphatic epoxies such as cyclohexene oxide and the ERLTM and UVRTM series type of binders available from Dow Chemical, Midland, MI, such as vinylcyclohexene oxide, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, bis- (3,4-epoxycyclohexyl) adipate and 2- (3, 4-epoxycylclohexyl-5, 5-spiro- 3,4-epoxy) cyclohexene-meta-dioxane; also included are the glycidyl ether type epoxy binders such as propylene oxide, epichlorohydrin, styrene oxide, glycidol, the EPON, EPONEX, and HELOXY series type of epoxy binders available from Resolution
  • KRATON LIQUID POLYMERS such as L-207 available from Kraton Polymers, Houston, TX, epoxidized polybutadienes such as the POLY BD binders from Atofina, Philadelphia, PA, 1,4-butanediol diglycidyl ether, polyglycidyl ether of
  • phenolformaldehyde and for example DENTM epoxidized phenolic novolac binders such as DEN 431 and DEN 438 available from Dow Chemical Co., Midland MI, epoxidized cresol novolac binders such as ARALDITE ECN 1299 available from Vantico AG, Basel, Switzerland, resorcinol diglycidyl ether, and epoxidized polystyrene/polybutadiene blends such as the Epofriendz binders such as EPOFRIEND A1010 available from Daicel USA Inc., Fort Lee, NJ, and resorcinol diglycidyl ether.
  • DENTM epoxidized phenolic novolac binders such as DEN 431 and DEN 438 available from Dow Chemical Co., Midland MI
  • epoxidized cresol novolac binders such as ARALDITE ECN 1299 available from Vantico AG, Basel, Switzerland, resorcinol diglycidy
  • Higher molecular weight polyols include the polyethylene and polypropylene oxide polymers in the molecular weight (Mn) range of 200 to 20,000 such as the
  • Vinyl ether monomers can be methyl vinyl ether, ethyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, triethyleneglycol divinyl ether (RAPT-CURE DVE-3, available from International Specialty Products, Wayne, NJ), 1,4- cyclohexanedimethanol divinyl ether (RAPI-CURE CHVE, International Specialty
  • trimetylolpropane trivinyl ether available from BASF Corp. , Mount Olive, NJ
  • VECTOMER divinyl ether binders from Morflex, Greensboro, N. C. , such as VECTOMER 2010, VECTOMER 2020, VECTOMER 4010, and VECTOMER 4020, or their equivalent from other manufacturers. It is within the scope of this invention to use a blend of more than one vinyl ether binder.
  • the preferred epoxy binders include the ERL and the UVR type of binders especially 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, bis- (3,4- epoxycyclohexyl) adipate and 2- (3, 4-epoxycylclohexyl-5,5-spiro-3, 4-epoxy)
  • hydroxy-functional materials can be added.
  • the hydroxyl-functional component can be present as a mixture or a blend of materials and can contain mono-and polyhydroxyl containing materials.
  • the hydroxy-functional material is at least a diol.
  • the hydroxyl- functional material can aid in chain extension and in preventing excess crosslinking of the epoxy during curing, e. g., increasing the toughness of the cured composition.
  • useful hydroxyl-functional materials include aliphatic,
  • cycloaliphatic or alkanol-substituted arene mono-or poly-alcohols having from about 2 to about 18 carbon atoms and two to five, preferably two to four hydroxy groups, or combinations thereof.
  • Useful mono-alcohols can include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 1-pentanol, neopentyl alcohol, 3- pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-phenoxy ethanol, cyclopentanol,
  • cyclohexanol cyclohexylmethanol, 3-cyclohexyl-l-propanol, 2-norbornanemethanol and tetrahydrofurfuryl alcohol.
  • Polyols useful in the present invention include aliphatic, cycloaliphatic, or alkanol- substituted arene polyols, or mixtures thereof having from about 2 to about 18 carbon atoms and two to five, preferably two to four hydroxyl groups.
  • Examples of useful polyols include 1,2-ethanediol, 1,2-propanediol, 1,3- propanediol, 1,4-butanediol, 1,3- butanediol, 2-methyl-l, 3 -propanediol, 2, 2-dimethyl-l, 3- propanediol, 2-ethyl-l, 6- hexanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, glycerol, trimethylolpropane, 1,2, 6-hexanetriol, trimethylol ethane, pentaerythritol, quinitol, mannitol, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerine, 2- ethyl-2- (hydroxymethyl)-l,
  • Bi-functional monomers having both cationically polymerizable and free-radically polymerizable moieties in the same monomer are useful in the present invention, such as, for example, glycidyl methacrylate, or 2-hydroxyethyl acrylate.
  • a free radically polymerizable monomer such as an acrylate or methacrylate.
  • a free radically polymerizable monomer broadens the scope of obtainable physical properties and processing options.
  • two or more polymerizable monomers can be present in any proportion.
  • Suitable cationic photoinitiators are selected from organic onium cations, for example those described in photoinitiators for Free Radical Cationic & Anionic
  • diaryliodonium triarylsulfonium, carbonium and phosphonium, and most preferably I-, and S-centered onium salts, such as those selected from sulfoxonium, diaryliodonium, and triarylsulfonium, wherein "aryl” means an unsubstituted or substituted aromatic moiety having up to four independently selected substituents.
  • the quantum dot layer can have any useful amount of quantum dots, and in some embodiments the quantum dot layer can include from 0.1 to 10 wt.%, preferably 0.1 to 1 wt.%, quantum dots, based on the total weight of the quantum dot layer (dots, optional liquid carrier and polymeric binder).
  • the dispersion composition can also contain a surfactant (i.e., leveling agent), a polymerization initiator, and other additives, as known in the art.
  • the stabilized quantum dots, the stabilizing copolymer, the polymeric binder, fluorinated carrier fluid and surface modifying ligand of Formula IV are combined and subject to high shear mixing to produce a dispersion of the ligand functional quantum dots in the polymer matrix.
  • the matrix is chosen such there is limited compatibility and the quantum dots form a separate, non-aggregating phase in the matrix.
  • the fluorinated carrier fluid enables separation and removal of any organic solvent.
  • the dispersion comprising droplets of stabilized nanoparticle and optional fluorochemical carrier fluid, are dispersed in the binder resin, is then coated and cured either thermally, free-radically, or both to lock in the dispersed structure and exclude oxygen and water from the dispersed quantum dots.
  • the curable composition When using a free-radically curable polymeric binder, the curable composition further comprises photoinitiators, in an amount between the range of about 0.1% and about 5% by weight.
  • photoinitiators include those known as useful for photocuring free-radically polyfunctional (meth)acrylates.
  • Exemplary photoinitiators include benzoin and its derivatives such as alpha-methylbenzoin; alpha-phenylbenzoin; alpha-allylbenzoin; alpha- benzylbenzoin; benzoin ethers such as benzil dimethyl ketal (e.g., "IRGACURE 651 " from BASF, Florham Park, NJ), benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether; acetophenone and its derivatives such as 2-hydroxy-2-methyl-l -phenyl- 1-propanone (e.g., "DAROCUR 1173" from BASF, Florham Park, NJ) and 1 -hydroxy cyclohexyl phenyl ketone (e.g., "IRGACURE 184" from BASF, Florham Park, NJ); 2-methyl-l-[4- (methylthio)phenyl]-2-(4-morpholinyl)-l-propanone (e
  • photoinitiators include, for example, pivaloin ethyl ether, anisoin ethyl ether, anthraquinones (e.g., anthraquinone, 2-ethylanthraquinone, 1- chloroanthraquinone, 1,4-dimethylanthraquinone, 1-methoxyanthraquinone, or benzanthraquinone), halomethyltriazines, benzophenone and its derivatives, iodonium salts and sulfonium salts, titanium complexes such as bis(eta5-2,4-cyclopentadien-l-yl)- bis[2,6-difluoro-3-(lH-pyrrol-l-yl) phenyl ]titanium (e.g., "CGI 784DC" from BASF,
  • halomethyl-nitrobenzenes e.g., 4-bromomethylnitrobenzene
  • mono- and bis-acylphosphines e.g., "IRGACURE 1700", “IRGACURE 1800”, “IRGACURE 1850”, and "DAROCUR 4265”
  • the curable composition may be irradiated with activating UV or visible radiation to polymerize the components preferably in the wavelengths of 250 to 500 nanometers.
  • UV light sources can be of two types: 1) relatively low light intensity sources such as blacklights that provide generally 10 mW/cm 2 or less (as measured in accordance with procedures approved by the United States National Institute of Standards and Technology as, for example, with a UVIMAPTM UM 365 L-S radiometer manufactured by Electronic Instrumentation & Technology, Inc., in Sterling, VA) over a wavelength range of 280 to 400 nanometers and 2) relatively high light intensity sources such as medium- and high- pressure mercury arc lamps, electrodeless mercury lamps, light emitting diodes, mercury- xenon lamps, lasers and the like, which provide intensities generally between 10 and 5000 mW/cm 2 in the wavelength rages of 320-390nm (as measured in accordance with procedures approved by the United States National Institute of Standards and Technology as, for example, with a PowerPuckTM radiometer
  • quantum dot article 10 includes a first barrier layer 32, a second barrier layer 34, and a quantum dot layer 20 between the first barrier layer 32 and the second barrier layer 34.
  • the quantum dot layer 20 includes a plurality of quantum dots 22 dispersed in a matrix 24.
  • the barrier layers 32, 34 can be formed of any useful material that can protect the quantum dots 22 from exposure to environmental contaminates such as, for example, oxygen, water, and water vapor.
  • Suitable barrier layers 32, 34 include, but are not limited to, films of polymers, glass and dielectric materials.
  • suitable materials for the barrier layers 32, 34 include, for example, polymers such as polyethylene terephthalate (PET); oxides such as silicon oxide, titanium oxide, or aluminum oxide (e.g., S1O2, S12O3, T1O2, or AI2O3); and suitable combinations thereof.
  • barrier films can be selected from a variety of constructions. Barrier films are typically selected such that they have oxygen and water transmission rates at a specified level as required by the application. In some embodiments, the barrier film has a water vapor transmission rate (WVTR) less than about 0.005 g/m 2 /day at 38°C. and 100% relative humidity; in some embodiments, less than about 0.0005 g/m 2 /day at 38°C. and 100% relative humidity; and in some embodiments, less than about 0.00005 g/m 2 /day at 38°C and 100% relative humidity.
  • WVTR water vapor transmission rate
  • the flexible barrier film has a WVTR of less than about 0.05, 0.005, 0.0005, or 0.00005 g/m 2 /day at 50 °C and 100% relative humidity or even less than about 0.005, 0.0005, 0.00005 g/m 2 /day at 85 °C and 100%) relative humidity.
  • the barrier film has an oxygen transmission rate of less than about 0.005 g/m 2 /day at 23°C and 90% relative humidity; in some embodiments, less than about 0.0005 g/m 2 /day at 23 °C and 90% relative humidity; and in some embodiments, less than about 0.00005 g/m 2 /day at 23 °C and 90% relative humidity.
  • Exemplary useful barrier films include inorganic films prepared by atomic layer deposition, thermal evaporation, sputtering, and chemical vapor deposition.
  • Useful barrier films are typically flexible and transparent.
  • useful barrier films comprise inorganic/organic.
  • Flexible ultra-barrier films comprising inorganic/organic multilayers are described, for example, in U.S. 7,018,713 (Padiyath et al.).
  • Such flexible ultra-barrier films may have a first polymer layer disposed on polymeric film substrate that is overcoated with two or more inorganic barrier layers separated by at least one second polymer layer.
  • the barrier film comprises one inorganic barrier layer interposed between the first polymer layer disposed on the polymeric film substrate and a second polymer layer 224.
  • each barrier layer 32, 34 of the quantum dot article 10 includes at least two sub-layers of different materials or compositions.
  • such a multi-layered barrier construction can more effectively reduce or eliminate pinhole defect alignment in the barrier layers 32, 34, providing a more effective shield against oxygen and moisture penetration into the matrix 24.
  • the quantum dot article 10 can include any suitable material or combination of barrier materials and any suitable number of barrier layers or sub-layers on either or both sides of the quantum dot layer 20. The materials, thickness, and number of barrier layers and sub-layers will depend on the particular application, and will suitably be chosen to maximize barrier protection and brightness of the quantum dots 22 while minimizing the thickness of the quantum dot article 10.
  • each barrier layer 32, 34 is itself a laminate film, such as a dual laminate film, where each barrier film layer is sufficiently thick to eliminate wrinkling in roll-to-roll or laminate manufacturing processes.
  • the barrier layers 32, 34 are polyester films (e.g., PET) having an oxide layer on an exposed surface thereof.
  • the quantum dot layer 20 can include one or more populations of quantum dots or quantum dot materials 22.
  • Exemplary quantum dots or quantum dot materials 22 emit green light and red light upon down-conversion of blue primary light from a blue LED to secondary light emitted by the quantum dots. The respective portions of red, green, and blue light can be controlled to achieve a desired white point for the white light emitted by a display device incorporating the quantum dot article 10.
  • Exemplary quantum dots 22 for use in the quantum dot articles 10 include, but are not limited to, CdSe with ZnS shells.
  • Suitable quantum dots for use in quantum dot articles described herein include, but are not limited to, core/shell luminescent nanocrystals including CdSe/ZnS, InP/ZnS, PbSe/PbS, CdSe/CdS, CdTe/CdS or CdTe/ZnS.
  • the luminescent nanocrystals include an outer ligand coating and are dispersed in a polymeric matrix.
  • Quantum dot and quantum dot materials 22 are commercially available from, for example, Nanosys Inc., Milpitas, CA.
  • the quantum dot layer 20 can have any useful amount of quantum dots 22, and in some embodiments the quantum dot layer 20 can include from 0.1 wt% to 1 wt% quantum dots, based on the total weight of the quantum dot layer 20.
  • the quantum dot materials can include quantum dots dispersed in a liquid carrier.
  • the liquid carrier can include an oil such as an amino-silicone oil.
  • the quantum dot layer 20 can optionally include scattering beads or particles. These scattering beads or particles have a refractive index that differs from the refractive index of the matrix material 24 by at least 0.05, or by at least 0.1. These scattering beads or particles can include, for example, polymers such as silicone, acrylic, nylon, and the like, or inorganic materials such as T1O2, SiOx, AlOx, and the like, and combinations thereof. In some embodiments, including scattering particles in the quantum dot layer 20 can increase the optical path length through the quantum dot layer 20 and improve quantum dot absorption and efficiency. In many embodiments, the scattering beads or particles have an average particle size from 1 to 10 micrometers, or from 2 to 6 micrometers. In some embodiments, the quantum dot material 20 can optionally include fillers such fumed silica.
  • the scattering beads or particles are Tospearl 1 TM 120A, 130A, 145A and 2000B spherical silicone resins available in 2.0, 3.0, 4.5 and 6.0 micron particle sizes respectively from Momentive Specialty Chemicals Inc., Columbus, Ohio.
  • the matrix 24 of the quantum dot layer 20 can be formed from an polymeric binder or binder precursor that adheres to the materials forming the barrier layers 32, 34 to form a laminate construction, and also forms a protective matrix for the quantum dots 22.
  • the matrix 24 is formed by curing or hardening an adhesive composition including an epoxy amine polymer and an optional radiation-curable methacrylate compound.
  • the present disclosure is directed to a method of forming a quantum dot film article 100 including coating a polymeric binder composition including quantum dots on a first barrier layer 102 and disposing a second barrier layer on the quantum dot material 104.
  • the method 100 includes polymerizing (e.g., radiation curing) a radiation curable polymeric binder to form a fully- or partially cured quantum dot material 106 and optionally thermally polymerizing the binder composition to form a cured polymeric binder 108.
  • step 106 is omitted.
  • the binder composition can be cured or hardened by heating. In other embodiments, the binder composition may also be cured or hardened by applying radiation such as, for example, ultraviolet (UV) light. Curing or hardening steps may include UV curing, heating, or both. In some example embodiments that are not intended to be limiting, UV cure conditions can include applying about 10 mJ/cm 2 to about 4000 mJ/cm 2 of UVA, more preferably about 10mJ/cm 2 to about 1000 mJ/cm 2 of UVA. Heating and UV light may also be applied alone or in combination to increase the viscosity of the binder composition, which can allow easier handling on coating and processing lines.
  • UV ultraviolet
  • the binder composition may be cured after lamination between the overlying barrier films 32, 34.
  • the increase in viscosity of the binder composition locks in the coating quality right after lamination.
  • the cured binder increases in viscosity to a point that the binder composition acts as a pressure sensitive adhesive (PSA) to hold the laminate together during the cure and greatly reduces defects during the cure.
  • PSA pressure sensitive adhesive
  • the radiation cure of the binder provides greater control over coating, curing and web handling as compared to traditional thermal curing.
  • the binder composition forms polymer network that provides a protective supporting matrix 24 for the quantum dots 22.
  • Ingress is defined by a loss in quantum dot performance due to ingress of moisture and/or oxygen into the matrix 24.
  • the edge ingress of moisture and oxygen into the cured matrix 24 is less than about 1.25 mm after 1 week at 85°C, or about less than 0.75 mm after 1 week at 85°C, or less than about 0.5 mm after 1 week at 85°C.
  • oxygen permeation into the cured matrix is less than about 80 (cc.mil)/(m 2 day), or less than about 50 (cc.mil)/(m 2 day).
  • the water vapor transmission rate of the cured matrix should be less than about 15 (20g/m 2 .mil.day), or less than about 10 (20g/m 2 .mil.day).
  • the thickness of the quantum dot layer 20 is about 80 microns to about 250 microns.
  • FIG. 3 is a schematic illustration of an embodiment of a display device 200 including the quantum dot articles described herein.
  • the display device 200 includes a backlight 202 with a light source 204 such as, for example, a light emitting diode (LED).
  • the light source 204 emits light along an emission axis 235.
  • the light source 204 (for example, a LED light source) emits light through an input edge 208 into a hollow light recycling cavity 210 having a back reflector 212 thereon.
  • the back reflector 212 can be
  • the backlight 202 further includes a quantum dot article 220, which includes a protective matrix 224 having dispersed therein quantum dots 222.
  • the protective matrix 224 is bounded on both surfaces by polymeric barrier films 226, 228, which may include a single layer or multiple layers.
  • the display device 200 further includes a front reflector 230 that includes multiple directional recycling films or layers, which are optical films with a surface structure that redirects off-axis light in a direction closer to the axis of the display, which can increase the amount of light propagating on-axis through the display device, this increasing the brightness and contrast of the image seen by a viewer.
  • the front reflector 230 can also include other types of optical films such as polarizers.
  • the front reflector 230 can include one or more prismatic films 232 and/or gain diffusers.
  • the prismatic films 232 may have prisms elongated along an axis, which may be oriented parallel or perpendicular to an emission axis 235 of the light source 204.
  • the prism axes of the prismatic films may be crossed.
  • the front reflector 230 may further include one or more polarizing films 234, which may include multilayer optical polarizing films, diffusely reflecting polarizing films, and the like.
  • the light emitted by the front reflector 230 enters a liquid crystal (LC) panel 280.
  • LC liquid crystal
  • Numerous examples of backlighting structures and films may be found in, for example, U.S. 8848132 (O'Neill et al.). Examples
  • UV Barrier film 2 mil (50 micrometer) barrier film obtained as FTB-M-50 from 3M Company (St. Paul, MN).
  • the methyl ester F(CF(CF3)CF 2 0) a CF(CF3)C(0)OCH3, wherein the variable a has an average value of about 6, was prepared by metal fluoride-initiated oligomerization of hexafluoropropylene oxide (HFPO) in diglyme solvent according to the method described in U.S. Patent No. 3,250,808 (Moore et al.), the description of which is incorporated herein by reference. The product was purified by distillation to remove low-boiling components.
  • HFPO hexafluoropropylene oxide
  • Example 1 by sodium borohydride reduction to the alcohol followed by allylation with allyl bromide according to the method described in US Patent Publication 20140287248 (Flynn et. al.), the description of which is incorporated herein by reference.
  • Example 1 Preparation of HFPO-derived ether succinic acid
  • Example 3 Preparation of a green InP/ZnS dispersion in FC-70.
  • a mixture of 20g of the polymer of Example 1 and 40g of FC-70 was degassed using bubbling nitrogen and then placed in an inert atmosphere glovebox.
  • a 250 mL round bottomed flask was charged with 15 mL of the above solution and 120 mL of green growth solution.
  • the flask was fitted with an overhead stirrer and placed on a hot plate held at 80 °C.
  • the mixture was stirred vigorously for 1 hour, after which it was allowed to cool and separate into 2 layers.
  • the colorless top layer was removed, and the bottom fluorinated layer was washed twice with 30 mL of heptane, stirring for 5 minutes during each washing. Residual heptane was removed under low pressure, yielding a haze-free orange-green oil with an OD of approximately 80.
  • Example 4 Preparation of a red InP/ZnS dispersion in FC-70.
  • the quantum dot concentrate dispersions of Examples 5-8 were placed in septum-capped quartz cuvettes with a cell of width 1 cm and length 0.1 cm. These cells were placed in a lamp between two 15 watt Phillips TLD fluorescent bulbs with a spectral output in the blue range. The lamp was covered with reflective foil and turned on. At specified times, 12 ⁇ ⁇ aliquots of concentrate were removed from the cuvettes and diluted with 4 mL of FC-70. Quantum yields of these dilute dispersions were measured using an absolute PL Quantum Yield Spectrometer CI 1347 (Hamamatsu Corporation, Middlesex, New Jersey). The results are shown in Figure 5.
  • Example 11 The quantum dot dispersion of Example 11 (1.37 g) and the dispersion of example 12 (0.79 g) were added to the acrylate polymeric binder of example 10 (20 g).
  • the solution of dot concentrate and binder was mixed with a cowles-blade mixer for 3 minutes at 1400 rpm. This mixture was coated between two 2 mil (- 51 ⁇ ) barrier films at a thickness of 100 ⁇ using a knife coater.
  • the coatings were then cured with ultraviolet (UV) radiation using a CLEARSTO E UV LED lamp at 385 nm for 60 seconds.
  • UV ultraviolet
  • the formulation preparation, coating, and curing was carried out inside a VAC- Atmosphere glove box.
  • the quantum dot dispersion of Example 13 (1.37 g) and the dispersion of example 14 (0.79 g) were added to the acrylate polymeric binder of example 10 (20 g).
  • the solution of dot concentrate and binder was mixed with a cowles-blade mixer for 3 minutes at 1400 rpm. This mixture was coated between two 2 mil (- 51 ⁇ ) barrier films at a thickness of 100 ⁇ using a knife coater.
  • the coatings were then cured with ultraviolet (UV) radiation using a CLEARSTO E UV LED lamp at 385 nm for 60 seconds.
  • UV ultraviolet
  • Coatings were tested initially, after 1 week of aging at 85 °C, and after 1 week of aging in a lifetime screening box (aged at a temperature of 85 °C and under illumination with a light intensity of 152 watts/steradian/m 2 ). Initial results are shown in Table 5. Table 6 shows aging results after 1 week 85 °C. Lifetime screening box results are shown in Table 7.
  • Color, luminance, and %efficiency were quantified by placing the constructed QDEF film into a recycling system ( Figure 4) and measuring with a colorimeter 302 available from Photo Research, Inc. (Chatsworth, CA) under the trade designation PR650.
  • the QDEF under investigation was placed on a gain cube 304 with a blue LED light.
  • a micro-replicated brightness enhancement film available from 3M (St. Paul, MN) under the trade designation VIKUITI BEF was placed over the QDEF. A white point was achieved in this recycling system.

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Abstract

L'invention concerne des points quantiques et articles à points quantiques stabilisés par un copolymère fluorochimique possédant des groupes stabilisants pendants arsine, stibine ou phosphine; et des groupes fluorochimiques pendants.
PCT/US2017/017152 2016-02-17 2017-02-09 Points quantiques à copolymères fluorés stabilisants WO2017142782A1 (fr)

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